Predicting the phase equilibria of petroleum fluids with the SAFT‐VR approach

The SAFT-VR equation of state is combined with a semi-continuous thermodynamic approach to model several synthetic and crude oil systems. In our approach, the oil fractions are defined by a continuous distribution that is then represented as discrete pseudo-components using the Gaussian quadrature method. The SAFT-VR parameters for the pseudo-components are obtained from simple linear relationships that were defined in earlier work, which allows the approach to be easily applied to undefined oil systems. Good agreement between the theoretical predictions and experimental data is obtained for bubble point pressure calculations of several gas condensates and the solubility of gases such as methane, ethane, and carbon dioxide in several crude oils. ! 2007 American Institute of Chemical Engineers AIChE J, 53: 720‐731, 2007

[1]  M. Radosz,et al.  Phase behavior of reservoir fluids: VI. Cosolvent effects on bitumen fractionation with supercritical CO2 , 1994 .

[2]  Karen S. Pedersen,et al.  SRK-EOS calculation for crude oils , 1983 .

[3]  Mohammad R. Riazi,et al.  Prediction of the Composition of Petroleum Fractions , 1980 .

[4]  G. Hirasaki,et al.  Modeling of Asphaltene Phase Behavior with the SAFT Equation of State , 2003 .

[5]  Stanley H. Huang,et al.  Equation of state for small, large, polydisperse, and associating molecules: extension to fluid mixtures , 1991 .

[6]  C. McCabe,et al.  Predicting the solubility of xenon in n-hexane and n-perfluorohexane: a simulation and theoretical study , 2002 .

[7]  George Jackson,et al.  SAFT: Equation-of-state solution model for associating fluids , 1989 .

[8]  Horst Kehlen,et al.  Continuous thermodynamics of multicomponent systems , 1985 .

[9]  L. Verlet,et al.  Perturbation Theory and Equation of State for Fluids , 1969 .

[10]  A. Gil-Villegas,et al.  Asphaltene Precipitation in Crude Oils: Theory and Experiments , 2004 .

[11]  Stanley H. Huang,et al.  Equation of state for small, large, polydisperse, and associating molecules , 1990 .

[12]  M. Wertheim,et al.  Fluids with highly directional attractive forces. III. Multiple attraction sites , 1986 .

[13]  O. Mullins,et al.  The overriding chemical principles that define asphaltenes , 2001 .

[14]  Mohammad R. Riazi,et al.  Prediction of molecular-type analysis of petroleum fractions and coal liquids , 1986 .

[15]  J. Prausnitz,et al.  Phase equilibria for mixtures containing very many components. development and application of continuous thermodynamics for chemical process design , 1985 .

[16]  M. Radosz,et al.  Phase behavior of reservoir fluids. III : Molecular lumping and characterization , 1991 .

[17]  T. Reed,et al.  Applied statistical mechanics : thermodynamic and transport properties of fluids , 1973 .

[18]  A. Galindo,et al.  Predicting the High-Pressure Phase Equilibria of Binary Mixtures of Perfluoro-n-alkanes + n-Alkanes Using the SAFT-VR Approach , 1998 .

[19]  M. Radosz,et al.  Phase behavior of reservoir fluids IV: Molecular weight distributions for thermodynamic modeling , 1991 .

[20]  K. E. Starling,et al.  Equilibrium Thermodynamic Properties of the Mixture of Hard Spheres , 1971 .

[21]  P. Cummings,et al.  Anomalies in the Solubility of Alkanes in Near-Critical Water , 2003 .

[22]  W. E. Culham,et al.  Experimental and Theoretical Studies on the Fluid Properties Required for Simulation of Thermal Processes , 1981 .

[23]  R. Reid,et al.  The Properties of Gases and Liquids , 1977 .

[24]  J. Prausnitz,et al.  Flash calculations for continuous or semicontinuous mixtures by use of an equation of state , 1985 .

[25]  Clare McCabe,et al.  SAFT-VR modelling of the phase equilibrium of long-chain n-alkanes , 1999 .

[26]  M. Wertheim,et al.  Fluids with highly directional attractive forces. I. Statistical thermodynamics , 1984 .

[27]  George Jackson,et al.  Statistical associating fluid theory for chain molecules with attractive potentials of variable range , 1997 .

[28]  M. Radosz,et al.  Phase behavior of reservoir fluids V: SAFT model of CO2 and bitumen systems , 1991 .

[29]  J. Barker,et al.  Perturbation Theory and Equation of State for Fluids: The Square‐Well Potential , 1967 .

[30]  J. Barker,et al.  What is "liquid"? Understanding the states of matter , 1976 .

[31]  Amparo Galindo,et al.  Study of the high pressure phase behaviour of CO2+n-alkane mixtures using the SAFT-VR approach with transferable parameters , 2002 .

[32]  B. Han,et al.  Phase equilibria of the CO2–Jiangsu crude oil system and precipitation of heavy components induced by supercritical CO2 , 1999 .

[33]  A. Teja,et al.  Prediction of dew points of semicontinuous natural gas and petroleum mixtures. 1. Characterization by use of an effective carbon number and ideal solution predictions , 1987 .

[34]  George Jackson,et al.  A statistical associating fluid theory for electrolyte solutions (SAFT-VRE) , 2001 .

[35]  Further evaluation of the Shariati-Peters-Moshfeghian C7+ characterization method , 2001 .

[36]  George Jackson,et al.  SAFT-VRE: Phase Behavior of Electrolyte Solutions with the Statistical Associating Fluid Theory for Potentials of Variable Range , 1999 .

[37]  G. Jackson,et al.  Thermodynamics of Liquid Mixtures of Xenon with Alkanes: (Xenon + n-Butane) and (Xenon + Isobutane) , 2000 .

[38]  J. Prausnitz,et al.  Additions and Corrections - Flash Calculations for Continuous or Semicontinuous Mixtures Using an Equation of State. , 1986 .

[39]  J. Prausnitz,et al.  SOLUBILITIES OF METHANE, ETHANE AND CARBON DIOXIDE IN HEAVY FOSSIL-FUEL FRACTIONS , 1987 .

[40]  M. Radosz,et al.  Phase behavior of reservoir fluids II: Supercritical carbon dioxide and bitumen fractions , 1990 .

[41]  Erich A. Müller,et al.  Molecular-Based Equations of State for Associating Fluids: A Review of SAFT and Related Approaches , 2001 .

[42]  M. Wertheim Fluids of dimerizing hard spheres, and fluid mixtures of hard spheres and dispheres , 1986 .

[43]  Clare McCabe,et al.  Modelling the phase behaviour and excess properties of alkane + perfluoroalkane binary mixtures with the SAFT-VR approach , 2005 .

[44]  D. Peng,et al.  A New Two-Constant Equation of State , 1976 .

[45]  R. A. Behrens,et al.  The Use of Semicontinuous Description To Model the C7+ Fraction in Equation of State Calculations , 1988 .

[46]  J. Barker,et al.  Perturbation theory and liquid mixtures , 1970 .

[47]  Amparo Galindo Lowri A. Davies Alej The thermodynamics of mixtures and the corresponding mixing rules in the SAFT-VR approach for potentials of variable range , 1998 .

[48]  M. Wertheim,et al.  Thermodynamic perturbation theory of polymerization , 1987 .

[49]  H. Mauser Liquids and Liquid Mixtures. , 1961 .

[50]  G. Jackson,et al.  On the liquid mixtures of xenon, alkanes and perfluorinated compounds , 2001 .

[51]  M. Wertheim,et al.  Fluids with highly directional attractive forces. II. Thermodynamic perturbation theory and integral equations , 1984 .

[52]  Equilibrium vaporization of oils by the chain-of-rotators group contribution equation of state , 1991 .

[53]  A. Galindo,et al.  Predicting the High-Pressure Phase Equilibria of Binary Mixtures of n-Alkanes Using the SAFT-VR Approach , 1998 .

[54]  J. Vera,et al.  Method to Calculate the Solubilities of Light Gases in Petroleum and Coal Liquid Fractions on the Basis of Their P/N/A Composition , 2005 .

[55]  A. Galindo,et al.  PREDICTION OF PHASE EQUILIBRIA FOR REFRIGERANT MIXTURES OF DIFLUOROMETHANE(HFC-32), 1,1,1,2-TETRAFLUOROETHANE (HFC-134A), AND PENTAFLUOROETHANE (HFC- 125A) USING SAFT-VR , 1998 .

[56]  A. Shariati,et al.  Bubble-Point Pressures of Some Selected Methane + Synthetic C6+ Mixtures , 1998 .

[57]  Zevi W. Salsburg,et al.  Hard sphere equation of state in the close-packed limit , 1971 .

[58]  George Jackson,et al.  New reference equation of state for associating liquids , 1990 .

[59]  A. Shariati,et al.  Bubble point pressures of some selected carbon dioxide + synthetic C6+ mixtures , 1998 .

[60]  Mahmood Moshfeghian,et al.  A systematic approach to characterize gas condensates and light petroleum fractions , 1999 .

[61]  G. Jackson,et al.  Thermodynamics of Liquid Mixtures of Xenon with Alkanes: (Xenon + Ethane) and (Xenon + Propane) , 2000 .

[62]  G. Jackson,et al.  The theoretical prediction of the cricital points of alkanes, perfluoroalkanes, and their mixtures using bonded hard-sphere (BHS) theory , 1996 .

[63]  G. Jackson,et al.  Predicting the High-Pressure Phase Equilibria of Methane + n-Hexane Using the SAFT-VR Approach , 1998 .

[64]  Amparo Galindo† and,et al.  Theoretical Examination of the Global Fluid Phase Behavior and Critical Phenomena in Carbon Dioxide + n-Alkane Binary Mixtures , 2002 .

[65]  M. Wertheim,et al.  Fluids with highly directional attractive forces. IV. Equilibrium polymerization , 1986 .

[66]  A. Shariati,et al.  Bubble Point Pressures of Some Petroleum Fractions in the Presence of Methane or Carbon Dioxide , 1998 .

[67]  Clare McCabe,et al.  Examining the Adsorption (Vapor-Liquid Equilibria) of Short-Chain Hydrocarbons in Low-Density Polyethylene with the SAFT-VR Approach , 2001 .